KR20060049248A - Liquid crystal aligning agent for inkjet application - Google Patents

Abstract

This invention provides the liquid crystal aligning agent which implements the performance of a liquid crystal aligning film, and a favorable coating film state, when apply | coated with an inkjet apparatus.

The liquid crystal aligning agent for inkjet coating of this invention contains the polymer which has at least one of an amic acid repeating unit and its imidation repeating unit, and N-methylpyrrolidone which is its solvent.

Liquid crystal aligning film, liquid crystal aligning agent, inkjet apparatus, imidation repeating unit

Description

Liquid Crystal Alignment Agent for Inkjet Coating {Liquid Crystal Aligning Agent for Inkjet Application}

[Patent Document 1] Japanese Unexamined Patent Publication No. 2000-204250

[Patent Document 2] Japanese Unexamined Patent Publication No. 2003-215915

The present invention relates to a liquid crystal aligning agent for inkjet printing. More specifically, it relates to a liquid crystal aligning agent which exhibits excellent coating stability and film thickness uniformity when applied to a substrate by an inkjet printing method.

At present, a liquid crystal aligning film containing polyimide or the like is formed on the surface of the substrate on which the transparent conductive film is provided to form a substrate for a liquid crystal display element, and two of them are disposed to face each other to form a liquid crystal layer in the gap to form a sandwich structure. After forming a cell, the so-called TFT liquid crystal panel which operated this liquid crystal display element by TFT drive is widely used instead of the conventional CRT monitor.

As a liquid crystal display element, the so-called twisted nematic (TN) which used the nematic type liquid crystal which has positive dielectric anisotropy as a liquid crystal, and made the longitudinal axis of a liquid crystal molecule twist 90 degrees continuously from one board | substrate to the other board | substrate. TN type liquid crystal display elements having a type liquid crystal cell are known. In addition, STN (Super Twisted Nematic) liquid crystal display elements having a higher contrast and less visual dependence than TN liquid crystal display elements, vertically aligned liquid crystal display elements, and transverse electric field drive type liquid crystal display elements have been developed.

It is the liquid crystal aligning film which controls the orientation of a liquid crystal in these liquid crystal display elements. After a liquid crystal aligning film apply | coats the liquid crystal aligning agent containing the polyamic-acid solution which is a precursor of polyimide, the polyimide solution soluble in a solvent, etc. to a board | substrate by the flex printing method, bakes this, and forms a resin film, it forms a liquid crystal on this, It is obtained by providing an orientation capability.

In recent years, however, in the flex printing method, the trouble of maintenance of the printing plate has been a problem, such as the need to replace the printing plate depending on the substrate. In the inkjet printing method, there is an advantage that the maintenance of the printing plate is not necessary, the pattern setting of printing is free, and the like, and the cost reduction and yield improvement of the liquid crystal panel are expected.

The liquid crystal aligning agent requires performances, such as voltage retention characteristic, low afterimage characteristic, and high reliability, in addition to the orientation regulation force of a liquid crystal. Moreover, the arbitrary pretilt angle (tilt angle with respect to the board | substrate of a liquid crystal molecule) developability is required according to the kind of liquid crystal display element. On the other hand, although the inkjet printing method has advantages such as cost reduction and yield improvement of the liquid crystal panel, the discharge stability in the liquid crystal aligning agents proposed in Patent Documents 1 and 2 is realized, but film thickness uniformity, There was a problem that the edge sharpness was insufficient. In addition, Patent Document 2 does not contain N-methylpyrrolidone due to the limitation of the nozzle material, and contains at least one or more of γ-butyrolactone and butyolocellosolve, the total content of which is contained in the entire solvent. Although it is disclosed that it should contain 90 weight% or more with respect to it, Recently, as a result of the improvement of the material of a nozzle, the nozzle which is good even if the liquid crystal aligning agent containing N-methylpyrrolidone is used has been developed. On the other hand, in order to improve the film thickness uniformity and the sharpness of the film edge by the inkjet coating method until the quality of the actual liquid crystal display is satisfied, at least one or more of γ-butyrolactone and butyolocellosolve is contained, and It was insufficient as the liquid crystal aligning agent which total content contains 90 weight% or more with respect to the whole solvent.

Moreover, in the inkjet coating method, it is necessary to eject a liquid crystal aligning agent at high speed from a fine nozzle, and the viscosity characteristic of a liquid crystal aligning agent becomes an important factor. That is, it is necessary to have little resistance and excellent fluidity when a strong external force is applied to the solution. In addition, the surface tension and viscosity characteristics of the solution become important factors for controlling the shape of the droplets after the impact on the substrate. By controlling these to an optimum value, the surface uniformity of the film after baking can be ensured, and the liquid crystal aligning film which has stable performance can be obtained. Although the liquid crystal aligning agent needs control of a film thickness after baking according to a use and a purpose, adjustment of solid content concentration is mentioned as one of these control methods. Although control of solid content concentration normally affects a viscosity characteristic and surface tension characteristic, it is necessary to adjust solid content concentration, maintaining these characteristics.

On the other hand, the required performance as a liquid crystal aligning film becomes higher and higher, and high voltage retention, high liquid crystal alignability, low residual DC, etc. are calculated | required.

As a result of earnestly researching from the above circumstances, in the present invention, by mixing a polymer having a specific structure and a specific solvent, the solid content concentration, viscosity characteristics, surface tension characteristics, solvent content is adjusted, and film thickness uniformity in the inkjet printing apparatus. It succeeded in manufacture of the liquid crystal aligning agent which is excellent in the sharpness of a film | membrane and a film edge, and can obtain a high performance liquid crystal panel, and reached this invention.

That is, the objective of this invention is providing the liquid crystal aligning agent which implements the performance of a liquid crystal aligning film, and a favorable coating film state, when apply | coated with an inkjet apparatus.

Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are polymers having at least one repeating unit selected from the group consisting of repeating units represented by the following general formula (1a) and repeating units represented by the following general formula (1b) and N- as a solvent thereof. It is achieved by the liquid crystal aligning agent for inkjet coating which contains methylpyrrolidone.

In formula, Q <^1> is a divalent organic group, P <^1> becomes a tetravalent organic group, but at least one part of P <^1> is group represented by following General formula (1c).

In the formula, Q ² is a divalent organic group, P ² is a tetravalent organic group, except that at least a part of P ² is a group represented by the following general formula (1c).

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The said polymer component is melt | dissolved in a solvent, and the liquid crystal aligning agent of this invention is comprised. As a polymer component in this invention, the polyamic acid which has a repeating unit represented by the said Formula (1a), the imidation polymer which has a repeating unit represented by the said Formula (1b), and the amic acid prepolymer which has a repeating unit represented by the said Formula (1a) And a block copolymer having an imidized prepolymer having a repeating unit represented by the above formula (1b), and the like, and these may be used alone or in combination of two or more thereof. When using in combination of 2 or more type, it is preferable to mix and use a polyamic acid and an imidation polymer.

In the above, a polyamic acid is obtained by making tetracarboxylic dianhydride and diamine react, and an imidation polymer is obtained by dehydrating and ring-closing the said polyamic acid. The imidized polymer may not be dehydrated or closed in 100% of the repeating units, or may be less than 100% in proportion (hereinafter referred to as "imidization rate") of the repeating units having the imide ring in all the repeating units. .

P ¹ in Formula 1a and P ² in Formula 1b are all tetravalent organic groups. At least some of these tetravalent organic groups, that is, some to all, are tetravalent organic groups represented by the formula (1c). P ¹ and P ² are derived from tetracarboxylic dianhydride and correspond to a group in which two anhydride groups are removed from tetracarboxylic dianhydride. The tetravalent organic group represented by the said Formula (1c) is derived from 2,3,4-tricarboxycyclopentyl acetic dianhydride.

Further, Q ¹ in Formula 1a and Q ² in Formula 1b are both divalent organic groups. Q ¹ and Q ² are derived from diamine and correspond to a group obtained by removing two amino groups from diamine.

Tetracarboxylic dianhydride

The tetracarboxylic dianhydride used for the synthesis of the polyamic acid is a combination of 2,3,5-tricarboxycyclopentyl acetic dianhydride or this and other tetracarboxylic dianhydride. As a specific example of other tetracarboxylic dianhydride, it is 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl- 1,2,3,4- cyclobutane tetra, for example. Carboxylic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride Water, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2 , 4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexyltetracarboxylic dianhydride, cis-3,7-dibutylcycloocta-1,5-diene -1,2,5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6-dianhydride, 2,3,4, 5-tetrahydrofurantetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3 -Dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c]- Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl)- Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3 -Furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (te Trahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5 , 8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxo Tetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2 ] -Octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3,2,1] octane-2,4-dione-6-spiro-3'- Alicyclic tetracarboxylic dianhydrides such as (tetrahydrofuran-2 ', 5'-dione) and compounds represented by the following formulas (I) and (II);

<Formula I>

<Formula II>

In formula, R <^3> and R <^6> represents the divalent organic group which has an aromatic ring, R <^4> and R <^5> represent a hydrogen atom or an alkyl group, and two or more R <^4> and R <^5> may be same or different, respectively.

Aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride;

Pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenylsulfontetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3 ', 4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic Acid dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydrides, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydrides, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4 '-Biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphineoxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, Ethylene glycol bis (anhydrotrimelitate), propylene glycol bis (anhydro trimellitate), 1,4-butanediol-bis (anhydro trimellitate), 1,6-hexanediol-bis (anhydro Trimellitate), 1,8-octanediol-bis (anhydro trimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydro trimellitate), represented by the following Chemical Formulas 1 to 4 Aromatic tetracarboxylic dianhydrides, such as aromatic tetracarboxylic dianhydride which has a steroid skeleton shown, are mentioned. These tetracarboxylic dianhydrides are used individually by 1 type or in combination of 2 or more types.

Among these other tetracarboxylic dianhydrides, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride , 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 5- (2 , 5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2 , 5,6-tetracarboxylic dianhydride, 3,5,6-tricarbonyl-2-carboxynorbornane-2: 3,5: 6- dianhydride, 1,3,3a, 4,5, 9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5 , 9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3, 3a, 4,5,9b-hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3 Dion, vehicle [2,2,2] -octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3,2,1] octane-2,4-dione-6 -Spiro-3 '-(tetrahydrofuran-2', 5'-dione), a compound represented by the following formulas 5 to 7 of the compound represented by the formula (I), of the compound represented by the formula (II) Compound represented by, butanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyl Sulfontetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride is preferable, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, fatigue Mellitic dianhydride is more preferred. These other tetracarboxylic dianhydrides are used individually by 1 type or in combination of 2 or more types.

The use ratio of the 2,3,5-tricarboxycyclopentylacetic dianhydride with respect to the total tetracarboxylic dianhydride is preferably 1 mol% or more, more preferably 20-100 mol%, particularly 50-100 mol%. desirable.

<Diamine>

As a diamine used for the synthesis | combination of a polyamic acid, p-phenylenediamine, m-phenylenediamine, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenylethane, 4, 4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'- Diaminobiphenyl, 4,4'-diaminobenzanilide, 4,4'-diaminodiphenylether, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 3,4 '-Diaminodiphenylether, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 2,2-bis [4- (4-amino Phenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-amino Oxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2 , 7-diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetrachloro- 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diamino Biphenyl, 1,4,4 '-(p-phenyleneisopropylidene) bisaniline, 4,4'-(m-phenyleneisopropylidene) bisaniline, 2,2'-bis [4- (4 -Amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 4,4'-bis [( Aromatic diamines such as 4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl;

1,1-methacrylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine , 1,4-diaminocyclohexane, isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindenylenedimethylenediamine, tricyclo [6.2.1.02,7] -undecylenedimethyl Aliphatic and alicyclic diamines such as diamine and 4,4'-methylenebis (cyclohexylamine);

2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5 , 6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine , 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino -6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6- Diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6-diaminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5 -Diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8-diamino-6-phenylphenanthtridine, 1,4-diaminopiperazine 2 primary amino groups in the molecule, such as 3,6-diaminoacridine, bis (4-aminophenyl) phenylamine, and other than the primary amino group Diamines having a small atom;

And diamino organosiloxane represented by the following general formula (III). These diamines can be used individually or in combination of 2 or more types.

<Formula III>

In formula, R <^7> represents a C1-C12 hydrocarbon group, two or more R <^7> may be same or different, p is an integer of 1-3 and q is an integer of 1-20.

Among them, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 2,2'-dimethyl-4,4'-diaminobiphenyl, 1, 5-diaminonaphthalene, 2,7-diaminofluorene, 4,4'-diaminodiphenylether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediisopropylidene) bisaniline, 1,4-cyclohexanediamine, 4,4'-methylenebis (cyclohexylamine ), 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2, 4-diaminopyrimidine, 3,6-diaminoacridine and the like are preferable.

In order to have an effective pretilt angle expression property in the liquid crystal aligning agent of this invention, some or all of Q <^1> in said Formula (1a) and / or Q <^2> in said Formula (1b) is a following formula Q-1 and following formula Q It is preferable to use diamines (hereinafter also referred to as "specific diamines") having groups represented by the following general formula Q-1 or the following general formula Q-2 so as to be at least one group represented by -2. These specific diamines are used individually by 1 type or in combination of 2 or more types.

<Formula Q-1>

Wherein X is a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S- or an arylene group, R ¹ is an alkyl group having 10 to 20 carbon atoms, It is a monovalent organic group which has a C4-C40 alicyclic skeleton, or a monovalent organic group which has a C6-C20 fluorine atom.

<Formula Q-2>

Wherein two X's are each independently a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S- or an arylene group, and R ² is 4 carbon atoms It is a divalent organic group which has an alicyclic skeleton of 40 to 40.

In the above formula Q-1, as the alkyl group having 10 to 20 carbon atoms represented by R ¹ , for example, n-decyl group, n-dodecyl group, n-pentadecyl group, n-hexadecyl group, n-octade Practical groups, n-eicosyl groups, etc. are mentioned.

In addition, R ¹ and an organic group having an alicyclic skeleton having a carbon number of 4 to 40 represented by R ² in the general formula Q-2 in the above formulas Q-1, for example, cyclobutane, cyclopentane, cyclohexane, Groups having an alicyclic skeleton derived from a cycloalkane such as cyclodecane; Groups having a steroid skeleton such as cholesterol and cholestanol; The group which has bridge | crosslinked alicyclic skeleton, such as norbornene and adamantane, etc. are mentioned. Among them, particularly preferred are groups having a steroid skeleton. The organic group having the alicyclic skeleton may be a group substituted with a halogen atom, preferably a fluorine atom or a fluoroalkyl group, preferably a trifluoromethyl group.

Further, a group having a fluorine atom having 6 to 20 carbon atoms represented by R ¹ in the general formula Q-1, for example, n- hexyl, n- octyl, n- having a carbon number of at least 6, such as a straight chain group An alkyl group; Alicyclic hydrocarbon groups having 6 or more carbon atoms such as a cyclohexyl group and a cyclooctyl group; The group by which one part or all hydrogen atoms in organic groups, such as a C6 or more aromatic hydrocarbon group, such as a phenyl group and a biphenyl group, were substituted by fluoroalkyl groups, such as a fluorine atom or a trifluoromethyl group, is mentioned.

In addition, X in Formula Q-1 and Formula Q-2 is a single bond, -O-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, -S- or aryl It's Rengi. As an arylene group, a phenylene group, a tolylene group, a biphenylene group, a naphthylene group, etc. are mentioned, for example. Among these, particularly preferably, they are groups represented by -O-, -COO-, and -OCO-.

As a specific example of the diamine which has group represented by the said General formula Q-1, dodecaneoxy-2, 4- diamino benzene, pentadecaneoxy-2, 4- diamino benzene, hexadecaneoxy-2, 4- dia Minobenzene, an octadecaneoxy-2, 4- diamino benzene, and the compound represented by following General formula (9)-(14) are mentioned as a preferable thing.

Moreover, as a specific example of the diamine which has a group represented by the said General formula Q-2, the diamine represented by following General formula (15)-(17) is mentioned as a preferable thing.

Among these, particularly preferred are compounds represented by the formulas (9), (10), (13), (14) and (15).

Although the use ratio with respect to the total diamine amount of a specific diamine changes also with the magnitude | size of the pretilt angle to express, in the case of TN type and STN type liquid crystal display elements, it is 0-5 mol%, and In this case, 5 to 100 mol% is preferable.

Synthesis of Polyamic Acid

The use ratio of the tetracarboxylic dianhydride and the diamine provided in the synthesis reaction of the polyamic acid is preferably a ratio in which the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents relative to 1 equivalent of the amino group of the diamine. For example, the ratio is 0.3 to 1.2 equivalents.

The synthesis reaction of the polyamic acid is carried out in an organic solvent, for example, under a temperature condition of -20 ° C to 150 ° C, preferably 0 to 100 ° C.

The organic solvent is not particularly limited as long as it can dissolve the polyamic acid synthesized. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Aprotic polar solvents such as dimethyl sulfoxide, γ-butyrolactone, tetramethyl urea and hexamethylphosphortriamide; Phenol solvents, such as m-cresol, xylenol, a phenol, and a halogenated phenol, are mentioned. Moreover, it is preferable that the usage-amount ((alpha)) of an organic solvent is an amount such that the total amount ((beta)) of tetracarboxylic dianhydride and a diamine compound becomes 0.1-30 weight% with respect to the total amount ((alpha) + (beta)) of a reaction solution. .

In the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, and the like, which are poor solvents of polyamic acid, can be used in combination without causing precipitation of polyamic acid. As a specific example of such a poor solvent, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethylene glycol, propylene glycol , 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy Propionate, ethyl ethoxy propionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene Glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono Methyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichloro Butane, trichloroethane, chlorbenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like.

As described above, a reaction solution obtained by dissolving the polyamic acid is obtained. The reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and polyamic acid can be obtained by drying the precipitate under reduced pressure. In addition, the polyamic acid can be purified by dissolving the polyamic acid again in an organic solvent and subsequently depositing it in a poor solvent once or several times.

<Synthesis of imidized polymer>

An imidation polymer can be synthesize | combined by dehydrating and ring-closing part or all of the said polyamic acid. Preferable imidation ratio is 40 mol% or more, Especially preferably, it is 70 mol% or more. By using the polymer whose imidation ratio is 40 mol% or more, the liquid crystal aligning agent with which the liquid crystal aligning film with short residual image removal time can be formed is obtained.

The dehydration ring closure of the polyamic acid may be carried out by (i) a method of heating the polyamic acid, or (ii) by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to the solution, and heating it as necessary. Is done.

The reaction temperature in the method of heating the polyamic acid of said (i) becomes like this. Preferably it is 50-200 degreeC, More preferably, it is 60-170 degreeC. When reaction temperature is less than 50 degreeC, dehydration ring-closure reaction does not fully advance, and when reaction temperature exceeds 200 degreeC, the molecular weight of the imidation polymer obtained may fall.

On the other hand, in the method of adding a dehydrating agent and a dehydrating ring-closure catalyst to the solution of polyamic acid of said (ii), acid anhydrides, such as an acetic anhydride, a propionic anhydride, a trifluoroacetic anhydride, can be used as a dehydrating agent, for example. Although the usage-amount of a dehydrating agent changes with a desired imidation ratio, it is preferable to set it as 0.01-20 mol with respect to 1 mol of repeating units of a polyamic acid. As the dehydration ring closure catalyst, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used, for example. However, it is not limited to these. It is preferable that the usage-amount of a dehydration ring-closure catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents used. The imidation ratio can be increased as the usage-amount of the above-mentioned dehydrating agent and dehydrating ring closure agent increases. Moreover, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid as an organic solvent used for dehydration ring-closure reaction is mentioned. And the reaction temperature of dehydration ring-closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. Moreover, the imidated polymer obtained can be refine | purified by performing the operation similar to the purification method of polyamic acid with respect to the reaction solution obtained in this way.

<Terminal modified polymer>

The polymer used in the present invention may be a terminal modified form having a controlled molecular weight. By using this terminal modified polymer, the effect of this invention can be improved, and the coating characteristic of a liquid crystal aligning agent can be improved. Such a terminally modified polymer can be synthesized by adding an acid anhydride, a monoamine compound, a monoisocyanate compound and the like to the reaction system when synthesizing the polyamic acid. Here, examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, and the like. Can be. As the monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decyl Amines, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine etc. are mentioned. Moreover, as a monoisocyanate compound, phenyl isocyanate, naphthyl isocyanate, etc. are mentioned, for example.

<Viscosity of Polymer>

It is preferable that the value of the viscosity ((eta)) of the polymer obtained as mentioned above exists in the range of 5-15 mPa * s within the range of 1-5 weight% of solid content concentration.

<Block copolymer>

The above-mentioned block copolymer as a polymer component used for this invention synthesize | combines the amic acid prepolymer which has an amino group or an acid anhydride group at the terminal, and the imidization prepolymer which has an acid anhydride group or an amino group at the terminal, respectively, and each prepolymer A block copolymer can be obtained by combining the terminal amino group and the acid anhydride group. The synthesis method of the amic acid prepolymer is the same as the synthesis method of the polyamic acid described above, and the synthesis method of the imidized prepolymer is the same as the synthesis method of the imidized polymer described above. In addition, selection of the functional group which has a terminal can be performed by adjusting the quantity of tetracarboxylic dianhydride and diamine at the time of polyamic-acid synthesis | combination.

<Liquid crystal aligning agent>

The said polymer component is melt | dissolved and contained in the solvent, and the liquid crystal aligning agent of this invention is comprised. As the solvent, an organic solvent is used.

The temperature at the time of manufacturing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 0 degreeC-200 degreeC, More preferably, it is 20 degreeC-60 degreeC.

As an organic solvent which comprises the liquid crystal aligning agent of this invention, the mixture of N-methylpyrrolidone and the other solvent illustrated as what is used for the synthesis reaction of this and a polyamic acid is mentioned, A polyamic acid is synthesize | combined reaction The poor solvent illustrated as what can be used together can be suitably selected, and can be used together. In particular, preference is given to using a mixture of N-methyl-2-pyrrolidone or N-methyl-2-pyrrolidone γ-butyrolactone and / or butylcellosolve. Moreover, these mixed solvent and another poor solvent can also be mixed and used. At this time, content of N-methyl- 2-pyrrolidone is 10 weight% or more with respect to the whole solvent. Preferably, the butyl cellosolve comprises preferably at least 5% by weight, particularly preferably at least 10% by weight, based on the total solvent.

Solid content concentration in the liquid crystal aligning agent of this invention is selected in consideration of viscosity, volatility, etc., Preferably it is the range of 1 to 5 weight%. That is, although the liquid crystal aligning agent of this invention is apply | coated to the board | substrate surface, and the coating film used as a liquid crystal aligning film is formed, when solid content concentration is less than a lower limit, the film thickness of this coating film becomes too thin and a favorable liquid crystal aligning film cannot be obtained, and solid content concentration is an upper limit. When exceeding, discharge stability from an inkjet coating apparatus will fall.

<Adhesion aid>

In the viewpoint of improving the adhesiveness to the surface of a board | substrate, the liquid crystal aligning agent of this invention may contain the functional silane containing compound or the epoxy group containing compound. As such a functional silane containing compound, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltree Ethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N- Trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecan, 10-triethoxysilyl-1,4,7-triazadecan, 9-trimethoxysilyl -3,6-diazanyl acetate, 9-triethoxysilyl-3,6-diazanyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl -3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimeth Oxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, etc. are mentioned.

As the epoxy group-containing compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglyci Dil ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3 , 5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycid Dylaminomethyl) cyclohexane, N, N, N ', N'- tetraglycidyl-4,4'- diaminodiphenylmethane, etc. are mentioned as a preferable thing. The compounding ratio of these functional silane containing compounds and an epoxy group containing compound becomes like this. Preferably it is 40 weight part or less, More preferably, it is 0.1-30 weight part with respect to 100 weight part of polymers.

<Liquid crystal display element>

The liquid crystal display element obtained using the liquid crystal aligning agent of this invention can be manufactured, for example by the following method.

(1) The liquid crystal aligning agent of this invention is apply | coated to the one surface of the board | substrate with which the patterned transparent conductive film is provided by the inkjet printing method, and a coating film is formed by heating a coating surface subsequently.

Here, as a board | substrate, For example, glass, such as float glass and a soda glass; The transparent substrate containing plastics, such as a polyethylene terephthalate, a polybutylene terephthalate, a polyether sulfone, a polycarbonate, can be used. ITO containing tin oxide _{(In 2 O 3 -SnO 2)} - NESA film (US PPG Company registered trademark), indium oxide including a transparent conductive film, the tin oxide (SnO _2), which is installed on one side of the substrate A film | membrane etc. can be used, The photo-etching method and the method of using a mask beforehand are used for patterning of these transparent conductive films. When apply | coating a liquid crystal aligning agent, in order to make adhesiveness of a board | substrate surface, a transparent conductive film, and a coating film more favorable, you may apply | coat a functional silane containing compound, a functional titanium containing compound, etc. previously on the said surface of a board | substrate. .

The heating temperature after apply | coating a liquid crystal aligning agent becomes like this. Preferably it is 80-300 degreeC, More preferably, it is 120-250 degreeC. In addition, although the liquid crystal aligning agent of this invention containing a polyamic acid forms the coating film used as an oriented film by removing an organic solvent after application | coating, it can also be made into a more imidized coating film by advancing dehydration ring closure by further heating. The film thickness of the coating film formed becomes like this. Preferably it is 0.001-1 micrometer, More preferably, it is 0.005-0.5 micrometer.

(2) The rubbing process which rubs the formed coating film surface in the fixed direction with the roll which rolled the cloth which consists of fibers, such as nylon, rayon, and cotton, for example is performed. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it becomes a liquid crystal aligning film.

Moreover, the ultraviolet-ray as shown by Unexamined-Japanese-Patent No. 6-222366 and Unexamined-Japanese-Patent No. 6-281937 to the liquid crystal aligning film formed by the liquid crystal aligning agent of this invention partially, for example. The resist film is partially formed on the surface of the liquid crystal alignment film subjected to the treatment such as changing the pretilt angle or by the rubbing treatment as shown in JP-A-5-107544 by irradiating with After removing the resist film after performing the rubbing treatment in the other direction, it is possible to improve the field of view characteristics of the liquid crystal display element by performing a process such as changing the liquid crystal alignment ability of the liquid crystal alignment film. In the case of the vertical alignment film, the above rubbing treatment is not necessary. The rubbing treatment is not necessary. The rubbing treatment is applied on a substrate on which projections and patterning electrodes for controlling the hardness direction of the liquid crystal molecules are applied and heated.

(3) As described above, two substrates on which the liquid crystal alignment film was formed were prepared, and the TN alignment film was disposed such that the two substrates face each other through a gap (cell gap) so that the rubbing direction in each liquid crystal alignment film was perpendicular or antiparallel. After bonding the peripheral part of two board | substrates with a sealing agent, liquid crystal is injected-filled in the cell gap partitioned by the board | substrate surface and the sealing agent, and an injection hole is sealed and a liquid crystal cell is comprised. And a liquid crystal display by bonding a polarizing plate to the outer surface of the liquid crystal cell, ie, the other surface side of each board | substrate which comprises a liquid crystal cell, so that the polarization direction may coincide or orthogonally cross with the rubbing direction of the liquid crystal aligning film formed in one side of the said board | substrate. The device is obtained.

Here, as the sealant, for example, an epoxy resin containing aluminum oxide spheres as a curing agent and a spacer can be used.

Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable, and for example, cifbase-based liquid crystals, subfamily clock liquid crystals, biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, ester-based liquid crystals, terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, and pyrimidine-based liquid crystals. Liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cuban type liquid crystal, etc. can be used. In addition, these liquid crystals are, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate, and trade names "C-15" and "CB-15" (manufactured by Merck). You can also use it, adding the chiral agent etc. which are sold. In addition, ferroelectric liquid crystals such as p-disiloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

Moreover, as a polarizing plate bonded to the outer surface of a liquid crystal cell, the polarizing plate which sandwiched the polarizing film called H film which absorbed iodine while extending | stretching polyvinyl alcohol between the cellulose acetate protective film, or the polarizing plate containing H film itself is mentioned. Can be.

<Example>

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited to these Examples.

The evaluation method in an Example is shown below.

[Inkjet coating property of liquid crystal aligning agent]

The liquid crystal aligning agent which prepared the solid content concentration to 3 weight% was apply | coated on the ITO board | substrate in the liquid amount which a dry film thickness becomes 60 nm using the apparatus of a JET-CM continuous inkjet printer (product made by Gigi Kenko Co., Ltd.). It was. Subsequently, it dried at 230 degreeC, and the unevenness | corrugation of a dry film was measured with the needle contact type film thickness meter, and when the difference of the maximum film thickness and the minimum film thickness is 7 nm or less, it was judged as favorable. This liquid amount and coating pressure were made constant, and adjustment of the dry film thickness was performed by adjusting the solid content concentration of a liquid crystal aligning agent.

[Surface tension measurement]

The measurement was performed using the surface tension measuring device of CBUP SURFACE TENSIOMETER A1 (manufactured by Kyogawa Chemical Co., Ltd.).

[Viscosity measurement]

It measured using the E-type viscosity measuring apparatus of VISCOMETER RE100 (Tokko Sangyo Co., Ltd. product).

[Orientation of Liquid Crystal]

The presence or absence of the abnormal domain at the time of turning on / off (applying / releasing) a voltage to a liquid crystal display element was observed with the polarization microscope, and the case where there was no abnormal domain was judged as favorable.

[Voltage retention rate of liquid crystal display element]

After applying a voltage of 5 V to the liquid crystal display element in an application time of 60 microseconds and a period of 167 milliseconds, the voltage retention after 167 milliseconds from the release of the application was measured. The measurement apparatus used VHR-1 by Toyo Technica Co., Ltd.

[Afterimage erasing time]

After applying a DC voltage of 10 V to the liquid crystal display for 2 hours, the application of the voltage was canceled, and the display screen was visually observed to measure the time until the afterimage on the screen was canceled after the application of the voltage was released. It was.

<Synthesis Examples 1 to 21>

The compound shown in following Tables 1-2 was added to N-methyl- 2-pyrrolidone in order of molar ratio shown in parentheses in order, and it was made to react at room temperature with 20% of solid content concentration for 6 hours.

TCA: 2,3,5-tricarboxycyclopentyl acetic dianhydride

CB: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

PMA: pyromellitic dianhydride

MTDA: 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan -1,3-dione

PDA: p-phenylenediamine

DDM: 4,4'-diaminodiphenylmethane

MTB: 2,2'-dimethyl-4,4'-diaminobiphenyl

ODA: Octadecylamine

PTS: bisaminopropyltetramethyldisiloxane (diamine represented by Formula III above)

Diamine (a): diamine represented by the formula (9)

Diamine (b): diamine represented by the formula (10)

Diamine (c): diamine represented by the formula (13)

Diamine (d): diamine represented by the formula (15)

<Synthesis Examples 22-37>

PAA 2-4, PAA 6-10, PAA 14-21 were diluted with N-methyl-2-pyrrolidone so that solid content concentration might be 5 weight%, and 5 mol of pyridine per mol of diamine used for each polyamic acid synthesis | combination. Solvent-soluble imidization polymers PI-1 to PI-17 were synthesized by adding an imidation catalyst of 1 to 1 mol and 3 to 1 mol of acetic anhydride and stirring at 110 ° C for 4 hours. The polymer solution was concentrated in an evaporator, and N-methyl-2-pyrrolidone was substituted for γ-butyrolactone by an operation of adding γ-butyrolactone to obtain an imidized polymer solution.

<Examples 1 to 9>

The polyamic acid obtained by the synthesis example 1 was melt | dissolved so that it might become solid content concentration (TSC) shown in Table 4 in the mixed solvent containing butyl cellosolve (BC) at the mixing ratio (weight ratio) shown in Table 4 below. This solution was filtered using the filter of 1 micrometer of pore diameters, and the liquid crystal aligning agent of this invention was manufactured. The solution viscosity and surface tension at this time are shown in Table 4.

Each obtained liquid crystal aligning agent was apply | coated to the glass substrate with an ITO film | membrane using a JET-CM type | mold inkjet printer (product made by Giki Kenko Co., Ltd.), and it dried at 230 degreeC for 10 minutes, and obtained the coating film. The applicability | paintability of the liquid crystal aligning agent was evaluated, and the film thickness of the obtained coating film was measured. The results are shown in Table 4 together.

<Evaluation Example>

After applying an epoxy resin adhesive containing aluminum oxide spheres with a diameter of 5.5 µm to the outer edges of the pair of coating film forming substrates obtained in Example 1, the pair of liquid crystal sandwiching substrates were laminated so as to face the liquid crystal alignment film surface to face each other, and the adhesive was cured. I was. Subsequently, after filling a nematic liquid crystal (MLC-6608, Merck Co., Ltd.) between a pair of board | substrates from a liquid crystal inlet, the liquid crystal inlet is sealed with an acryl-type photocuring adhesive agent, a polarizing plate is bonded to both surfaces of a board | substrate outer side, and a liquid crystal is carried out. A display element was manufactured. The orientation of the obtained liquid crystal display device was good, and the voltage retention showed a high value of 99%. In addition, the afterimage erase time was 10 seconds.

<Reference Example>

A liquid crystal display device was manufactured in the same manner as in the evaluation example except that the coating method was spin coating. The orientation of the obtained liquid crystal display device was good, and the voltage retention showed a high value of 99%. In addition, the afterimage erase time was 10 seconds. Therefore, the liquid crystal display element obtained by the evaluation example had the performance similar to the liquid crystal display element obtained by the reference example.

<Examples 10 to 31>

Using the polyamic acid and imidation polymer shown in following Table 5, the liquid crystal aligning agent was produced like Example 1-9, and the liquid crystal display element was produced like the evaluation example. The applicability | paintability of the liquid crystal aligning agent was all favorable, and the orientation of the liquid crystal display element was also all favorable. The viscosity, surface tension, and coating property of a coating film of a liquid crystal aligning agent are shown together in Table 5.

<Examples 32 to 51>

Liquid crystal aligning agent was produced like Example 1-9 except using the polyamic acid and imidation polymer shown in following Table 6 by weight ratio 4: 1. Each obtained liquid crystal aligning agent was apply | coated to the glass substrate with an ITO film | membrane using a JET-CM type | mold inkjet printer (product made by Giki Kenko Co., Ltd.), and it dried at 230 degreeC for 10 minutes, and obtained the coating film. The rubbing process was performed by the rubbing machine which has the roll which wound the cloth made from rayon at the rotation speed of 400 rpm, the moving speed of 3 cm / sec of a stage, and the length of 0.4 mm which a hair tip enters. The substrate was immersed in ultrapure water for 1 minute and then dried for 5 minutes on a hot plate at 100 ° C to form a liquid crystal alignment film. Using this board | substrate, the liquid crystal display element was manufactured like the evaluation example. The applicability | paintability of the liquid crystal aligning agent was all favorable, and the orientation of the liquid crystal display element was also all favorable. The viscosity, surface tension, and coating property of a coating film of a liquid crystal aligning agent are shown together in Table 6.

According to the liquid crystal aligning film of this invention, the outstanding liquid crystal display element can be manufactured using the inkjet printing method.

The liquid crystal display element which has the liquid crystal aligning film of this invention can not only be used suitably for a TN type, STN type, and VA type liquid crystal display element but also SH (Super Homeotropic) type | mold, IPS (In by selecting the liquid crystal to be used, and -Plane Switching), OCB (Optically Compensated Bend), ferroelectric and antiferroelectric liquid crystal display elements, etc. can be used suitably.

Moreover, the liquid crystal display element which has the liquid crystal aligning film of this invention can be effectively used for various apparatuses, For example, display apparatuses, such as a table calculator, a wristwatch, a table clock, a coefficient display board, a word processor, a personal computer, a liquid crystal television, etc. Used for

Claims (4)

An inkjet coating comprising a polymer having at least one repeating unit selected from the group consisting of repeating units represented by the following formula (1a) and repeating units represented by the following formula (1b) and N-methylpyrrolidone as a solvent thereof Liquid crystal aligning agent. <Formula 1a>

(Wherein, Q ¹ is a divalent organic group, P ¹ is a tetravalent organic group, except that at least a portion of P ¹ is a group represented by the following formula (1c)): <Formula 1b>

(Wherein, Q ² is a divalent organic group, P ² is a tetravalent organic group, except that at least a portion of P ² is a group represented by the following formula (1c)) <Formula 1c>

The liquid crystal aligning agent for inkjet coating of Claim 1 whose content of N-methylpyrrolidone is 10 weight% or more. The liquid crystal aligning agent for inkjet coating according to claim 1, wherein the solid content concentration is in the range of 1 to 5% by weight, the viscosity is in the range of 5 to 15 mPa · s, and the surface tension is in the range of 30 to 45 dyne / cm. The compound according to claim 1, which is selected from the group consisting of ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, dipropylene glycol dialkyl ether and diethylene glycol dialkyl ether. The liquid crystal aligning agent for inkjet coating containing 10 weight% or more of 1 or more types of other solvent which become further.